Preparation of ethyl fluosulfonate



Patented Oct. 7, 1947 OFFICE PREPARATION. OF ETHYL FLUQSULFONATE Carl B.Linn, Riverside, Ill., assignor to Universal Oil Products Company,Chicago, 111., a corporation of Delaware No Drawing. ApplicationFebruary 23, 1946, Serial No. 649,745

Claims. 1

This invention relates to a process for preparing an ester offluosulfonic acid and particularly for preparing ethyl fluosulfonate.

An object of this invention is to prepare ethyl fluosulfonate.

One specific embodiment of the present invention relates to a processfor preparing ethyl fluosulfonate which comprises reacting ethylfluoride and fluosulfonic acid.

A further embodiment of this invention relates to a process forpreparing ethyl fluosulfonate which comprises reacting ethyl fluorideand fluosulfonic acid at a temperature of from about 30 to about 50 C.

Previously, ethyl fiuosulfonate was prepared in yields of not more thanabout 30% of the theoretical by the action of fluosulfonic acid upondiethyl ether or upon ethyl alcohol. This method described by Meyer andSchramm, Z. anorg. allgem. Chem, 206, 24 (1932) is illustrated by thefollowing equation:

When starting with ethyl alcohol the reaction used by Meyer and Schrammis illustrated by the following equation:

I have found that ethyl fluoride reacts with fluosulfonic acid at atemperature of from about --30 to about 50 C. and preferably at atemperature of from about to about +10 C. to give 64% or more of thetheoretical yield of ethyl fiuosulfonate according to the equation:

.My process is carried out in a suitable reactor such as a copperreactor provided with means for effecting stirring or agitation andprovided with cooling means such as immersion in a bath of ice andwater. mospheric pressure or at a superatmospheric pressure which isgenerally not in excess of 100 atmospheres.

The process may be carried out in batch or continuous types ofoperation. Also, hydrogen fluoride formed in the process may be reactedwith ethylene to produce ethyl fluoride, the latter then being reactedwith an additional quantity of fluosulfonic acid to form the desiredethyl fluosulfonate.

Ethyl fluosulfonate is useful as an intermediate in organic synthesisand it may be employed also as an insecticide, toxic spray, or a solventMy process is effected at at 2 for the separation of hydrocarbons andother organic compounds.

The following example is given to show results obtained in my processalthough these data should not be misconstrued to limit unduly the broadscope of the invention.

During a period of two hours, 18.7 grams of ethyl fluoride was passedslowly into 81 grams of fluosulfonic acid maintained at a temperature of0 C. in a glass reactor. Severe etching occurred in the glass reactor,this giving evidence a of the liberation of hydrogen fluoride accordingto the above equation. All of the ethyl fluoride was absorbed by thefluosulfonic acid and then the reaction mixture was treated withsupercooled ice until water could be added to the mixture withoutfurther evolution of heat. A colorless oil which was heavier than waterseparated from the resultant mixture. This oil after being washed withwater and dried over calcium chloride weighed 34 grams. of the dried oildistilled at 56-57 C. at a pressure of mm. of mercury, it waswater-white in color, had a refractive index, n of 1.3494 and a specificgravity, D of 1.28. This colorless oil had a pungent odor, was insolublein water and in sulfuric acid, although it is a substituted ester of thelatter. It etched glass upon standing in contact therewith for a fewhours. These physical properties and behavior of the colorless oilcorresponded to those of ethyl fiuosulfonate as recorded by Meyer andSchramm for the product that they obtained in 30% yield by the action offiuosulfonic acid upon diethyl ether.

The foregoing specification and example indicate the character and valueof this process, although it is not intended that either section shouldlimit unduly the broad scope of the invention.

I claim as my invention:

1. A process for preparing ethyl fluosulfonate which comprises reactingethyl fluoride and fluosulfonic acid.

2. A process for preparing ethyl fluosulfonate which comprises reactingethyl fluoride and fluosulfonic acid at a temperature of from about -30to about 50 C.

3. A process for preparing ethyl fluosulfonate which comprises reactingethyl fluoride and fluosulfonic acid at a temperature of from about 10to about +10 C.

4. A process for preparing ethyl fluosulfonate which comprises reactingethyl fluoride and fluosulfonic acid at a temperature of from about -30to about 50 C. and at a pressure of from substantially atmospheric toabout 100 atmos- REFERENCES CITED pheres. T

5. A combination process for preparing ethyl file i g g gg fz are ofrecord in the fluosulfonate which comprises reacting ethyl fluoride andfiuosulfonic acid at a, temperature of 5 U D STATES PATENTS from about-30 to about 50 C. to produce ethyl Number Name, Date u lfonateandhydrogen fluoride, reacting: said 1,510,425 Traube Sept. 30, 1924hydrogen fluoride with ethylene to produce ethyl V fluoride, andsupplying the latter to the first men-9; OTHER REFERENCES tioned p of ep s- 7 10 Levaillant et a1., Comptes rendus, 169, 140-2 CARL B-

